Circulating fluid bed (CFB) reactors are well known devices that can be used to carry out a variety of multiphase chemical reactions. In this type of reactor, a fluid (gas or liquid) is passed through a granular solid material at velocities high enough to suspend the solid and cause it to behave as though it were a fluid. Fluidization is maintained by means of fluidizing gas such as air, steam or reactant gas injected through a distributor (grid, spargers or other means) at the base of the reactor. CFB reactors are now used in many industrial applications, among which are catalytic cracking of petroleum heavy oils, olefin polymerization, coal gasification, and water and waste treatment. One major utility is in the field of circulating fluid bed combustors where coal or another high sulfur fuel is burned in the presence of limestone to reduce SOx emissions; emissions of nitrogen oxides is also reduced as a result of the relatively lower temperatures attained in the bed. Another application is in the fluidized bed coking processes known as fluid coking and its variant, Flexicoking™, both of which were developed by Exxon Research and Engineering Company.
Fluidized bed coking is a petroleum refining process in which heavy petroleum feeds, typically the non-distillable residue (resid) from fractionation, are converted to lighter, more useful products by thermal decomposition (coking) at elevated reaction temperatures, typically about 480 to 590° C., (about 900 to 1100° F.). The process is carried out in a unit with a large reactor vessel containing hot coke particles which are maintained in the fluidized condition at the required reaction temperature with steam injected at the bottom of the vessel with the average direction of movement of the coke particles being downwards through the bed. The heavy oil feed is heated to a pumpable temperature, mixed with atomizing steam, and fed through multiple feed nozzles arranged at several successive levels in the reactor. The steam is injected into a stripper section at the bottom of the reactor and passes upwards through the coke particles in the stripper as they descend from the main part of the reactor above. A part of the feed liquid coats the coke particles in the fluidized bed and subsequently decomposes into layers of solid coke and lighter products which evolve as gas or vaporized liquid. The light hydrocarbon products of the coking (thermal cracking) reactions vaporize, mix with the fluidizing steam and pass upwardly through the fluidized bed into a dilute phase zone above the dense fluidized bed of coke particles. This mixture of vaporized hydrocarbon products formed in the coking reactions continues to flow upwardly through the dilute phase with the steam at superficial velocities of about 1 to 2 meters per second (about 3 to 6 feet per second), entraining some fine solid particles of coke. Most of the entrained solids are separated from the gas phase by centrifugal force in one or more cyclone separators, and are returned to the dense fluidized bed by gravity through the cyclone diplegs. The mixture of steam and hydrocarbon vapor from the reactor is subsequently discharged from the cyclone gas outlets into a scrubber section in a plenum located above the reaction section and separated from it by a partition. It is quenched in the scrubber section by contact with liquid descending over scrubber sheds in a scrubber section. A pump around loop circulates condensed liquid to an external cooler and back to the top row of scrubber section to provide cooling for the quench and condensation of the heaviest fraction of the liquid product. This heavy fraction is typically recycled to extinction by feeding back to the fluidized bed reaction zone.
Components of the feed that are not immediately vaporized coat the coke particles in the reactor and are subsequently decomposed into layers of solid coke and lighter products which evolve as gas or vaporized liquids. During the contacting of the feed with the fluidized bed, some coke particles may become unevenly or too heavily coated with feed and during collision with other coke particles may stick together. These heavier coke particles may not be efficiently fluidized by the steam injected into the bottom of stripper section so that they subsequently pass downwards from the reactor section into the stripper section where they may adhere to and build up on the sheds in the stripper section, mainly on the uppermost rows of sheds. Conventionally, the stripper section has a number of baffles, usually termed “sheds” from their shape in the form of inverted channel sections extending longitudinally in several superimposed rows or tiers across the body of the stripper. The coke passes over these sheds during its downward passage through the stripper and is exposed to the steam which enters from the spargers at the bottom of the vessel below the sheds and is redistributed as it moves up the stripper. The solid coke from the reactor, consisting mainly of carbon with lesser amounts of hydrogen, sulfur, nitrogen, and traces of vanadium, nickel, iron, and other elements derived from the feed, passes through the stripper and out of the reactor vessel to a burner where it is partly burned in a fluidized bed with air to raise its temperature from about 480 to 700° C. (about 900° to 1300° F.), after which the hot coke particles are recirculated to the fluidized bed reaction zone to provide the heat for the coking reactions and to act as nuclei for the coke formation.
The Flexicoking™ process, also developed by Exxon Research and Engineering Company, is, in fact, a fluid coking process that is operated in a unit including a reactor and burner, often referred to as a heater in this variant of the process, as described above but also including a gasifier for gasifying the coke product by reaction with an air/steam mixture to form a low heating value fuel gas. The heater, in this case, is operated with an oxygen depleted environment. The gasifier product gas, containing entrained coke particles, is returned to the heater to provide a portion of the reactor heat requirement. A return stream of coke sent from the gasifier to the heater provides the remainder of the heat requirement. Hot coke gas leaving the heater is used to generate high-pressure steam before being processed for cleanup. The coke product is continuously removed from the reactor. In view of the similarity between the Flexicoking process and the fluid coking process, the term “fluid coking” is used in this specification to refer to and comprehend both fluid coking and Flexicoking except when a differentiation is required.
The stripping section of the fluid coking unit is located in the lower portion of the reactor. Coke particles from the reactor pass into the stripper where they are contacted with stripping steam from a sparger located at the bottom of the stripping section in order to remove hydrocarbon vapor phase products from the coke which is carried out of the bottom of the unit. As a result of the well-mixed nature of the reactor, a certain amount of coke entering the stripper is still coated with crackable hydrocarbon material. For this material, the stripper acts as an additional reaction section within which cracking and drying can occur. As this material progresses through the stripper, additional cracking reactions occur. For this reason, plug flow behavior is extremely desirable in the stripper in order to minimize the amount of crackable material sent to the burner or heater as hydrocarbon carry under, where it is effectively downgraded to coke. With basic fluid cokers, unlike Flexicokers, this phenomenon is not greatly disadvantageous as the quantities are small but in the case of Flexicokers, this material is sent to the heater, where it is exposed to a high temperature, oxygen poor environment. Unreacted material that enters the heater can crack to form a full range of vapor phase products. These products are then carried up into the heater overhead where they can condense onto surfaces resulting in capacity and/or run length limitations.
While hydrocarbon carry under is not a major concern for fluid coking units, these units do experience a different type of concern arising from operation of the stripper. Accumulation of deposits on the stripper sheds, which typically take on a characteristic shape by which they are named “shark fins”, makes the stripper vulnerable to reduced clearances that can interrupt the coke circulation in the stripper section, restrict fluidization of the coke in the reactor section and trap rubble spelled during a thermal cycle. If sufficiently large, the shark fins and can eventually lead to unplanned capacity loss or an unplanned reactor shutdown.
The dense fluid bed behaves generally as a well mixed reactor. However computational fluid dynamics model simulations and tracer studies have shown that significant amounts of wetted coke can rapidly bypass the reaction section and contact the stripper sheds. The mechanism postulated for the formation of the coke deposits is that a thin film of liquid (unconverted and partially converted feed material) on the coke causes the coke particle to stick loosely to other particles and/or the stripper shed surface. A portion of the wet film is converted to coke, binding the coke particles together. Over time, hydrocarbon species from the vapor phase condense in the interstices between the particles, creating deposits which are very hard and difficult to remove.
Current practice in fluid coking units is to raise reactor temperatures to accelerate the thermal cracking reactions. This enables the coke to dry more quickly and thereby reduce the amount of wetted coke that enters the stripper. However the higher reactor temperature increases the rate of recracking of the hydrocarbon vapors and reduces the C4+ liquid yield resulting in an economic debit.
Other attempts have previously been made to overcome this problem with varying degrees of success. For example, strippers have been fitted with steam spargers located underneath the stripper sheds, as reported by Hsiaotao Bi et al in “Flooding of Gas-Solids Countercurrent Flow in Fluidized Beds”, In Eng. Chem. Res. 2004, 43, 5611-5619. Sheds with apertures at set intervals have also been used, with spargers supplying a constant steam flow to the holes to reduce fouling.